The present invention relates to copolymers of ethylene having from 1 to 30 mol % of alkyl(meth)acrylates and, if desired, other comonomers, and having a residual comonomer content of less than. 0.5% by weight in the copolymer. It also relates to a process for preparing copolymers of this type in a combination of stirred autoclave and tubular reactor, and also to the use of the copolymers for preparing polyamide molding compositions.
Copolymers of ethylene with (meth)acrylates and/or (meth)acrylic acid are in principle known. For example, DE-A 32 34 492, DE-A 32 38 391 and DE-A 34 34 380 disclose copolymers of this type with different makeups and property profiles. They are used in particular as an additive for preparing impact-modified polyamide-based molding compositions with good processability. Molding compositions of this type are used, for example, to produce gear wheels and electrical switches via injection molding. For this type of application of ethylene-(meth)acrylate copolymers it is important that the incorporation of the comonomers into the copolymer is highly homogeneous. Fractions of the polymer which are low in comonomer, i.e. composed primarily of ethylene units, have an adverse effect on the properties of the resultant polyamide molding compositions, for example reducing their impact strength.
An important requirement placed upon ethylene-(meth)acrylate copolymers is a very low residual content of comonomers. Commercially available products comprise more than 0.5% by weight of free comonomers. When the polyamide molding composition is heated to the usual injection-molding temperatures of from 250 to 35 350xc2x0 C., this comonomer content evaporates and passes into the atmosphere. This causes undesirable odor in the workplace, and there may also be some degree of occupational health risk.
However, it is difficult to remove comonomers completely from the reaction product. Ethylene-(meth)acrylate copolymers are usually prepared by high-pressure polymerization in stirred autoclaves or tubular reactors (cf., for example, xe2x80x9cEthylene Polymersxe2x80x9d in Encyclopedia of Polymer Science and Engineering, Vol. 6, pp. 404 et seq.) or in a combination of both, as disclosed in EP-A 175 316. Depending on the type of reactor, the conversion here is up to 30% (stirred autoclave) or up to 35% (tubular reactor). Although (meth)acrylate monomers are more reactive than ethylene and are therefore favored for incorporation into the polymer during the polymerization, there are also unreacted comonomers in the polymer. Whereas any unreacted content of highly volatile ethylene can readily be removed in the product separation systems, unreacted content of higher-boiling comonomers, such as butyl acrylate, cannot be removed completely under these conditions, and they remain in the product. Even post-treatment with a stripping medium, such as N2, cannot remove them completely. None of the publications cited above discloses low-comonomer ethylene-(meth)acrylate copolymers or measures which can be used to reduce the residual comonomer content.
It is an object of the present invention to provide ethylene-(meth)acrylate copolymers with low residual comonomer content, and also a cost-effective process for preparing polymers of this type.
We have found that this object is achieved by means of copolymers of ethylene having from 1 to 30 mol % of alkyl(meth)acrylate and, if desired, other comonomers, and having a residual comonomer content of less than 0.5% by weight in the copolymer. A process for preparing copolymers of this type in a combination of stirred autoclave and downstream tubular reactor has been found, as has the use of the copolymers for preparing polyamide molding compositions.
The novel copolymers of ethylene incorporate from 1 to 30 mol %, preferably from 2 to 20 mol %, of alkyl(meth)acrylate comonomers in the polymer. Particularly suitable alkyl(meth)acrylates are (meth)acrylates of linear or branched C1-C8 alcohols. Examples of suitable esters are methyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate and tert-butyl(meth)acrylate. Butyl acrylate is very particularly suitable. It is also possible to incorporate a variety of alkyl(meth)acrylates into the polymer.
If desired, other comonomers may also be incorporated into the novel copolymers. Possible other comonomers are any of those which can be copolymerized with ethylene, in particular monoethylenically unsaturated comonomers. Examples of suitable comonomers are monoethylenically unsaturated carboxylic acids and derivatives of these, in particular acrylic, methacrylic, maleic and fumaric acid, amides, N-alkyl- or N,Nxe2x80x2-dialkylamides of unsaturated carboxylic acids, for example (meth)acrylamide and N,Nxe2x80x2-dimethyl(meth)acrylamide, mono- and diesters of maleic or fumaric acid, vinylcarboxylates, in particular esters of C1-C6 alkanecarboxylic acids, for example vinyl acetate, N-vinylformamide, N-vinylpyrrolidone, monoethylenically unsaturated alcohols, ketones, carbon monoxide, monomers containing epoxy groups and cyclic anhydrides. Particularly preferred other comonomers are acrylic acid and methacrylic acid.
The amount of other comonomers usually present is from 0 to 10 mol %, preferably from 1 to 5 mol %.
The novel copolymers comprise less than 0.5% by weight of unreacted comonomers, i.e. comonomers not incorporated into the copolymer. The proportion of unreacted comonomer is preferably less than 0.3% by weight.
The novel copolymers are preferably prepared by the novel process in a combination of a stirred autoclave with a downstream tubular reactor. Stirred autoclaves are pressure vessels provided with a stirrer for intensive mixing of the reactants. The length/diameter ratio is usually from 1 to 20. Tubular reactors are composed of pressure-tight tubes, usually bent into a serpentine shape, through which the material passes at high speeds. The connection between the two reactors may, for example, be a simple pressure-tight tubular connector. The length/diameter ratio is usually 5000 to 50,000. The copolymerization of the ethylene with (meth)acrylates and, if desired, other comonomers takes place at pressures of from 350 to 5000 bar, preferably from 1500 to 3000 bar.
The copolymerization of the ethylene with the (meth)acrylates and, if desired, other comonomers takes place in the presence of free-radical initiators. The initiators which can be used here are those which are also usually used for the homopolymerization of ethylene under high pressure, for example peroxides, hydroperoxides and azo compounds. Examples of this type of initiator are azobisisobutyronitrile, tert-butyl perpivalate, di-tert-butyl-peroxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl perisononanoate, tert-butyl perneodecanoate, methyl isobutyl ketone peroxide and dilauroyl peroxide. It is also possible to use mixtures of a variety of initiators.
The molecular weight of the copolymers may be adjusted in a known manner, using regulators. Examples of suitable regulators are hydrogen, hydrocarbons, such as propane or propene, and carbonyl compounds, such as propionaldehyde, acetone or methyl ethyl ketone.
The copolymerization is usually carried out without any solvent. This does not exclude the presence of small amounts of inert solvents usually used as solvents for initiators, for example mineral oils.
The polymerization takes place in two stages. The first polymerization stage takes place in the stirred autoclave and the second stage takes place in the tubular reactor. The polymerization temperature is selected by the skilled worker as a function of the desired product properties and of the comonomers used and also of any other comonomers which may be used. However, a decisive factor in the process is that the temperature in the second stage is higher than in the first stage. The desired polymerization temperature is set in the first stage, and the temperature in the second stage is above this. For typical monomer combinations, such as ethylene/butyl acrylate/acrylic acid, the temperature in the first stage is preferably less than 200xc2x0 C., and in the second stage it is greater than 200xc2x0 C. The temperature is particularly preferably from 180 to 200xc2x0 C. in the first stage and from 200 to 240xc2x0 C. in the second stage. The residence times and flow rates in the reactors here are preferably set so that the actual polymerization takes place primarily in the stirred autoclave, and then in the tubular reactor it is only the residual fractions of (meth)acrylate monomers and of other monomers which complete their polymerization. Since the reaction conditions in the stirred autoclave are highly homogeneous, the resultant polymers are very uniform in nature. The conversion in the first stage is generally at least 95% by weight (based on the total weight of final product) and in the second stage it is not more than 5% by weight. If the conversion in the second stage is higher, the resultant ethylene polymers can be disadvantageously low in comonomer. The conversion in the second stage is preferably only from 0.1 to 1% by weight. In the second stage it is in particular the residual fractions of comonomers present which are consumed in the reaction. This is therefore a xe2x80x9cchemical deodorizationxe2x80x9d.
The novel process gives copolymers which have a residual comonomer content of less than 0.5% by weight, in particular less than 0.3% by weight, and which nevertheless have a highly uniform nature. They are therefore highly suitable additives for preparing polyamide molding compositions with outstanding impact strength. The polyamide molding compositions produce only a low level of undesirable odor in thermoplastic processing to give moldings.